Classifications

• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61C—DENTISTRY; APPARATUS OR METHODS FOR ORAL OR DENTAL HYGIENE
  • A61C13/00—Dental prostheses; Making same
  • A61C13/0003—Making bridge-work, inlays, implants or the like
  • A61C13/0006—Production methods
  • A61C13/0019—Production methods using three dimensional printing
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61C—DENTISTRY; APPARATUS OR METHODS FOR ORAL OR DENTAL HYGIENE
  • A61C13/00—Dental prostheses; Making same
  • A61C13/0003—Making bridge-work, inlays, implants or the like
  • A61C13/0004—Computer-assisted sizing or machining of dental prostheses
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61C—DENTISTRY; APPARATUS OR METHODS FOR ORAL OR DENTAL HYGIENE
  • A61C13/00—Dental prostheses; Making same
  • A61C13/0003—Making bridge-work, inlays, implants or the like
  • A61C13/0006—Production methods
  • A61C13/0013—Production methods using stereolithographic techniques
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K6/00—Preparations for dentistry
  • A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
  • A61K6/884—Preparations for artificial teeth, for filling teeth or for capping teeth comprising natural or synthetic resins
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B33—ADDITIVE MANUFACTURING TECHNOLOGY
  • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
  • B33Y70/00—Materials specially adapted for additive manufacturing
  • B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/08—Processes
  • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/2805—Compounds having only one group containing active hydrogen
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
  • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
  • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
  • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
  • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
  • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
  • C08L75/04—Polyurethanes
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61C—DENTISTRY; APPARATUS OR METHODS FOR ORAL OR DENTAL HYGIENE
  • A61C2202/00—Packaging for dental appliances
  • A61C2202/01—Packaging for light-curable material
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B33—ADDITIVE MANUFACTURING TECHNOLOGY
  • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
  • B33Y80/00—Products made by additive manufacturing

Definitions

• the present invention relates generally to rapid prototyping systems, specifically, 3D printing systems for making multiple layered dental devices such as, for example, artificial teeth, dentures, splints, veneers, inlays, onlays, orthodontics, aligners, retainers, copings, frame patterns, crowns and bridges, models, appliances and the like. More particularly, it is related to the use of ink-jet, fused deposition modeling (FDM), selective laser sintering (SLS), stereolithography (SLA), digital light processing (DLP) or their combinations to build-up the dental devices as three-dimensional objects from many material systems and novel resin systems of this invention.
• FDM fused deposition modeling
• SLS selective laser sintering
• SLA stereolithography
• DLP digital light processing
• Ink-jet printing system dispenses materials through ink-jet printing head to form 3D object, which harden by cooling, polymerization, and light irradiation.
• FDM extrudes thermoplastic materials throughout nozzle to build 3D object.
• SLS uses laser as power source to sinter powdered materials to form solid objects.
• SLA using laser beam traces out the shape of each layer and hardens the photosensitive resin in a vat (reservoir or bath).
• DLP system builds three-dimensional objects by using the Digital Light Processor (DLP) projector to project sequential voxel planes into liquid resin, which then caused the liquid resin to cure.
• DLP Digital Light Processor
• rapid prototyping refers to a conventional manufacturing process used to make parts, wherein the part is built on a layer-by-layer basis using layers of hardening material.
• the part to be manufactured is considered a series of discrete cross- sectional regions which, when combined together, make-up a three-dimensional structure.
• the building-up of a part layer-by-layer is very different than conventional machining technologies, where metal or plastic pieces are cut and drilled to a desired shape.
• the parts are produced directly from computer-aided design (CAD) or other digital images. Software is used to slice the digital image into thin cross-sectional layers. Then, the part is constructed by placing layers of plastic or other hardening material on top of each other.
• CAD computer-aided design
• SLS Selective Laser Sintering
• SLA stereolithography
• FDM fused deposition modeling
• Digital Light Processing is another 3D Printing process very similar to stereolithography.
• the DLP technology was created in 1987 by Larry Hornbeck of Texas Instruments and became very popular in Projectors production. It uses digital micro mirrors laid out on a semiconductor chip.
• 3D inkjet, DLP and SLA all works with photopolymers.
• the difference between SLA and DLP processes is a different light source.
• DLP method projects sequential voxel planes into liquid resin, which then caused the liquid resin to cure.
• the material to be used for printing is liquid resin that is placed in the transparent resin container. The resin hardens quickly when affected by irradiation of light. The printing speed is pretty spectacular, especially with Carbon3D's CLIP (Continuous Liquid Interface Production) technology.
• methacrylate-based acrylics denture bases and teeth are made out of dough from the blending of PMMA or modified PMMA polymer powders with MMA or modified MMA liquids.
• Denture teeth are commonly made in a tooth manufacturer.
• Dental lab typically uses denture teeth and denture base material from manufacturer to make denture for patient.
• the initial step(s) commonly used in the making a denture by making a final impression of a patient's mouth.
• a cast (or record base) is made of the final impression of a patient's mouth.
• the cast is made of plaster.
• wax is shaped into the form of a denture base on the cast of the patient's mouth and artificial teeth are positioned into the denture base shaped wax.
• the denture base shaped wax with the artificial denture teeth is then positioned in an articulator.
• the artificial teeth in the denture base shaped wax are then articulated.
• the articulated denture base shaped wax with the artificial teeth is then positioned in a flask.
• the volume of the flask is filled with hardenable investment material, such as plaster.
• the investment material hardens the wax is eliminated, for example by heating the flask in boiling water, leaving the artificial teeth supported by the investment material and a denture base shaped mold cavity within the investment material.
• a denture base material is introduced into the mold cavity.
• the denture base material then hardens to form a denture.
• the process to make a denture is long, time-consuming and labor intensive.
• Preparation of full and partial dentures typically requires several dental office visits by each patient.
• the visits include labor intensive processes such as the construction of the baseplate and occlusion rims, wax try-in, invest the wax-up, wax removal and compression packing or pouring of denture base acrylic as described early.
• This traditional method typically resulted in a denture base containing homogeneous denture base material, which supported artificial denture teeth.
• a method of using light polymerizable wax like material reduces the dental office and laboratory visits and the labor involved in making the denture, which provides a process for making a denture, comprising: articulating artificial teeth while supported by polymerizable material, whereby a denture comprising said artificial teeth is provided without forming a mold for making tooth setup volume of a denture base. The process is completed without forming wax and without applying inorganic plaster to the artificial teeth. Multiple layers of denture base materials are possible and are included in the denture base by this method. Most recently, 3D printing systems have been using to make denture base and denture. Various 3D printing materials are used for 3D printing to make denture base and denture.
• a 3D printer uses acquired digital data to form materials to form final denture with denture base and denture teeth made from different materials.
• a 3D printer may also print material to form desired denture base, where commercially available artificial denture teeth are subsequently placed into printed cavities and bonded to this denture base. Separately, some denture teeth are also printed by a 3D printer and used to place into printed cavities and bonding to the printed denture base.
• Dentca's 3D Denture Base System scans the impression and builds denture base layer by layer using a stereolithographic laser printer and then bonds plastic teeth and final cures in a light chamber.
• FDM 3D printing method prints a denture using FDM printer with scanned or CAD data, which extrudes and deposits molten thermoplastic in layers to build denture from bottom up. Each layer of molten thermoplastic material is deposited on top of previous one and flattened slightly by the extrusion head. The layers are fused together to form final denture base.
• denture fabricated can be adjusted during final denture try-in to obtain desirable occlusion without the need of excessive of remaking, grinding, finishing and polishing.
• a denture fabricated where artificial denture teeth can be adjusted is highly desirable, which can avoid the need of additional tried-in step. It is also desirable the denture fabricated can be comfortable fit perfectly into oral cavity with rigid area to support artificial denture teeth and soft or relatively flexible contact surface to mucosal area for comfort and fit.
• denture bases are PMMA based acrylics.
• PMMA and MMA based denture bases have the disadvantage of being subject to brittle fracture due to the nature of PMMA. Rubber impact modified PMMA acrylics were used to improve their fracture toughness and impact strength.
• Full denture is typically formed from a rigid material since it is needed to support the artificial teeth chewing function without any movement during action.
• Flexible partial dentures typically made of flexible thermoplastics, such as Nylon 12, acetal resin, etc. are being commonly used for patients, which provide comfort due to their compliance and flexibility.
• the use of clasps enables to stabilize the artificial denture teeth in place.
• the resilience and flexibility of these denture bases are limited due to the need to support artificial denture teeth.
• Significantly improved resiliency of tissue contact surface is desirable without compromising the artificial denture teeth stability during mastication.
• a denture that provides a rigid ridge to support artificial denture teeth in position and resilient and flexible contact layer/area to patient's soft mucosal area for comfort and fit, which is more compatible to patient's oral cavity containing rigid ridge area and soft mucosal area. It is also desirable to have a partial denture that provides a rigid ridge to support artificial denture teeth in position, toughening clasps to stabilize the partial denture in place, and resilient and flexible contact layer/area to patient's soft mucosal area for comfort and fit, which is more compatible to patient's oral cavity containing remaining teeth, rigid ridge area and soft mucosal area.
• the printing methods and materials of this invention are not limited to the printing of denture, denture teeth or denture base, they can be used to print various dental devices. Their shades can be formed from clear to highly pigmented shade. For example, a multiple layered nightguard can be printed, where the hard and wear resistant top surface layer can effectively withstand wearing and grinding while flexible or resilient side or not occlusal contact part in nightguard can provide comfort, retention and easy insertion and easy removal for the patient.
• the denture base or denture tooth materials mentioned in this invention can be easily referred as dental materials, such as restorative materials, night guard materials, retainer materials, or aligner materials, etc.
• Leyden et al. US Patents 6,660,209 and 6,270,335 disclose an ink-jet printing method using commercial print heads having multiple orifices (jets) to selectively fire droplets of hot melt, radiation-curable material onto a substrate.
• Each orifice can be equipped with a piezoelectric element that causes a pressure wave to propagate through the material when electric current is applied.
• the print head moves along a scan path selectively depositing the flowable material onto the substrate.
• light radiation is used to cure the material.
• Yamane et al. US Patent 5,059,266 discloses an ink-jetting method, whereby a photosetting or thermosetting resin is jetted along a flight passage of the material to a stage to thereby laminate the material on the stage, changing at least one of a jetting direction of the material along the flight passage and a jetting amount of the material, thereby controlling a jetting operation of the material, and exposing the laminated material to light to cure the material, thereby forming the article.
• Rheinberger et al., US Patent 7,189,344 discloses a process for producing three- dimensional dental restorative parts, such as full or partial dental prosthesis, using ink-jet printers that are used in the ink-jet printing methods developed by MIT as described above.
• the process involves spraying a polymerizable material onto a base support in a layer-by-layer manner. Each layer of material is polymerized by a light source prior to the application of the next layer.
• the present invention provides novel high strength/toughness, resilient or high toughness liquid resin/composite systems for fabricating three-dimensional dental devices using the Inkjet, Digital Light Processor (DLP) projectors or stereolithography.
• This invention can also use many commercially available materials, such as polymerizable resins, thermoplastic materials, shape memory polymers, etc., their combinations and their combinations with liquid resin/composite systems of this invention and several early inventions of present inventor(s) for fabricating three-dimensional dental devices using the Inkjet, FDM, DLP, SLS, SLA or their combinations.
• FIGURE 1A is seen a schematic cross-sectional view of a denture base with two layered denture base materials.
• FIGURE 1 B is a schematic side cross-sectional view of a denture base comprising of two layers.
• FIGURE 1 D is another schematic side cross-sectional view of a denture base comprising of three layers.
• FIGURE 2A is seen a schematic cross-sectional view of a multiple layered denture containing two shaded layers of denture base and denture tooth with at least one layer shaded material(s).
• FIGURE 2B is seen a schematic side cross-sectional view of a multiple layered denture containing two shaded layers of denture base and denture tooth with at least one layer shaded material(s).
• FIGURE 2D is another schematic side cross-sectional view of a multiple layered denture containing two shaded layers of denture base and two shaded layers of denture tooth materials.
• FIGURE 2H is seen a schematic side cross-sectional view of a multiple layered denture containing multiple shaded layers of denture base and multiple shaded layers of denture tooth.
• FIGURE 2A is seen a schematic cross-sectional view of a multiple layered denture containing two layer denture base materials and at least one denture tooth material layer(s).
• FIGURE 2B is seen a schematic side cross-sectional view of a multiple layered denture containing two denture base material layers and at least one denture tooth material layer(s). Two layers of denture base materials may not have uniform thickness.
• Partially cured dental prosthesis can be fully cured by light, heat, the combination of light and heat to form final dental devices, such as dentures, partial dentures, nightguards, retainers, etc.
• Another one of the features of the multiple layered dental prosthesis of this invention is that it contains at least two layers of different materials in this dental device or prosthesis, e.g., denture made from at least two different 3D printing methods, such as FDM and DLP, DLP and SLA, DLP and SLS, FDM and SLS, inkjet and DLP, and many combinations.
• denture made from at least two different 3D printing methods, such as FDM and DLP, DLP and SLA, DLP and SLS, FDM and SLS, inkjet and DLP, and many combinations.
• a DLP printed denture base was subsequently located in SLS printer and tooth layer was formed by SLS method.
• a DLP printed denture base built from bottom up was subsequently irradiated with laser beam traced from above / tilted angle to build second denture base in a second liquid resin vat and additional denture base layer or denture tooth layer may be added in additional changed liquid resin vat as needed.
• Additional denture base layer(s) may be built. Then this can be washed and transferred into dentin shaded bath to build dentin layer on the surface of previous built shapes. If desired, additional dentin layer(s) may be built. After it is washed and transferred into an enamel bath, where an enamel layer is built thin layer by thin layer on the surface of previous built shapes and forms a final denture device with integral teeth on two or more layered denture base. If additional shades are desired, additional layers of different dentin and enamel shades or denture base and characterized denture base shades can be built similarly as described above. Nevertheless, a denture may be built by reversal steps, where teeth or enamel are built first and then denture base. Alternatively, layered denture base may be printed and then bonded to artificial denture teeth.
• a first layer of polymerizable (or polymeric) denture tooth material was printed on top of denture base to form a first denture tooth layer on denture base form, which is uncured, partially cured or fully cured to form first layer of denture tooth.
• another layer of polymerizable (or polymeric) denture tooth material was printed on top of first denture tooth layer and denture base to form a second denture tooth layer of denture form, which is uncured, partially cured or fully cured to form second denture tooth layer of denture at desired location. Additional layers might be printed as needed. In addition, additional final cure may be applied for this denture if needed. Nevertheless, a denture may be built by reversal steps, where teeth are built first and then denture base.
• a layer of polymerizable (or polymeric) denture tooth material was printed to form a first layer of denture tooth form, which is uncured, partially cured or fully cured to form first layer of denture tooth at desired location.
• a second layer of polymerizable (or polymeric) denture tooth material was printed on top of first layer denture tooth to form a second denture tooth layer of denture tooth form, which is uncured, partially cured or fully cured to form second layer of denture tooth at desired location. Additional layers might be printed as needed. Alternatively, additional final cure may be applied for this denture tooth if needed.
• a layer of polymerizable (or polymeric) denture tooth material was printed to form a first layer of denture tooth form, which is uncured, partially cured or fully cured to form first layer of denture tooth at desired location. Additional layers might be printed as needed. Subsequently, a first layer of polymerizable (or polymeric) denture base material (including composite) was printed on denture tooth to form a first denture base layer of denture form, which is uncured, partially cured or fully cured to form first layer of denture base at desired location.
• At least two polymerizable (or polymeric or the combination of polymerizable and polymeric) denture base materials (at least one of them forms shape memory polymeric layer) and at least one polymerizable (or polymeric or the combination of polymerizable and polymeric) denture tooth material (including composite) was printed to form a multiple layered denture, which is uncured, partially cured or fully cured. Additional final cure may be applied for this denture if needed.
• One layer of denture base at the tissue, at denture teeth side or both can be easily adjusted or reversed repeatedly as needed.
• a first layer of denture base is formed from the printing of a layer of shape memory polymeric (or polymerizable) material.
• a second layer of polymerizable (or polymeric) denture base material was printed on top of first layer denture base to form a second denture base layer of denture, which is uncured, partially cured or fully cured to form second layer of denture base at desired location.
• Additional layer of polymerizable (or polymeric) denture base material was printed to form another shape memory polymer layer in denture before the tooth layers.
• Both the contour of tissue side and the positions of denture teeth of denture can be adjusted repeatedly and independently once heated to a specific temperature or activated since the shape memory polymeric materials at tissue side and around denture teeth have different phase transition temperatures or different phase transition mechanisms.
• the invention provides multiple layered integral denture base with different performances for different layers, multiple layered integral artificial teeth with different performances for different layers, as well as multiple layered integral denture base and artificial teeth with different performances for different layers.
• the denture base and artificial tooth layers are preferably shaped by a 3D printing method in partially cured, fully cured or uncured stages.
• Epoxy compounds polymerize by ring-opening polymerization shrinks less and generate less polymerization stress due to the increase in excluded free-volume associated with the ring-opening process.
• Various epoxides or epoxy (meth)acrylates in combination with various diols such as 1 ,3-bis(3-glycidyloxypropyl)tetramethyldisiloxane, bisphenol A proxylate diglycidyl ether, bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate, 1 ,10 decanediol, 1 ,6- hexanediol, branched diol, aromatic diol, bisphenol A, proxylated bisphenol A, etc.
• Printable polymerizable dental materials compositions of the invention may include various inorganic and organic fillers, glass fillers, pigments, initiators, catalysts, stabilizers, various modifiers, surfactants, antimicrobial agents, antibiofilm agents, UV absorbing additives, thermal color stabilizers, thixotroping agents, plasticizers, rubber impact modifiers, antifungal agents, fibers or their combinations.
• Preferred stabilizers are butylated hydroxytoluene (BHT) and the methyl ether of hydroquinone (MEHQ), etc. It may also include compounds/filers to introduce radiopaque in the material. Many red fibers may be used to offer the benefits of esthetic appearance, such as the use of short red acetate fibers.
• the denture base and artificial tooth materials used here including dental composite materials may optionally include one or more additives that can include, without limitation, at least one filler (e.g., fibers, polymers, glass particles or otherwise), initiators, pigments, an inhibitor, or combinations thereof or others.
• at least one filler e.g., fibers, polymers, glass particles or otherwise
• initiators e.g., pigments, an inhibitor, or combinations thereof or others.
• the printable polymerizable dental materials and compositions of this invention may include one or more initiating systems to cause them to harden promptly.
• Light polymerizable dental compositions or composites preferably include a light sensitizer, for example 2,4,6- trimethylbenzoyldiphenylphosphine oxide, camphorquinone, or methyl benzoin which causes polymerization to be initiated upon exposure to activating wavelengths of light; and/or a reducing compound, for example tertiary amine.
• Photoinitiators selected from the class of acylphosphine oxides which include, for example, monoacyl phosphine oxide derivatives, bisacyl phosphine oxide derivatives, and triacyl phosphine oxide derivatives.
• acylphosphine oxides include, for example, monoacyl phosphine oxide derivatives, bisacyl phosphine oxide derivatives, and triacyl phosphine oxide derivatives.
• TPO 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide
• Cationic polymerization initiators diaryliodonium and triaryl sulfonium salts, such as 4- octyloxy-phenyl-phenyl iodonium hexafluoroantimonate (OPPI), can also be used, which initiates ring opening polymerization as well as volume expansion from phase change to reduce the polymerization shrinkage.
• Electron-transfer photosensitizers such as polynuclear aromatic compounds, their substituted analogues, carbazoles, phenothiazines, curcumin, and titanium- complex free radical initiator can also be added. Photoinitiators can be used are not limited to above examples.
• Polymerizable dental materials of the invention may include two or more initiating systems to cause them to harden promptly at different rates.
• Light curable polymerizable dental materials or composites preferably include at least two light sensitizers, for example camphorquinone/4-octyloxy-phenyl-phenyl iodonium hexafluoroantimonate (OPPI) and 2,4,6- trimethylbenzoyldiphenylphosphine oxide, which causes polymerization to be initiated upon exposure to activating wavelengths of light through free-radical polymerization and cationic ring opening polymerization at different rates.
• the polymerization stress generated in the first polymerization is effectively absorbed by second slow polymerized resin system.
• free-radical polymerization generates polymerization stress is significantly reduced due to free flow (or free mobility) of second cationic ring opening polymerization resin, which polymerizes and generates significantly less polymerization stress.
• Additional polymerization by heat, light or their combination offers much improved physical properties or performances. Additional examples may include at least a light curable initiator and at least a heat cure initiator, at least a self-curable initiator and at least a heat cure initiator, or at least a self-curable initiator and at least a light cure initiator.
• a room temperature or heat activating polymerizable denture base or artificial tooth materials are also preferably include a room temperature (chemical) or heat activating catalyst system.
• initiators include, but are not limited to, dibenzoyl peroxide (BPO), dilauroyl peroxide (LPO), t-butylhydroperoxide, cumene hydroperoxide, di-t-butyl peroxide, dicumyl peroxide, acetyl peroxide, 1 -benzyl-5-phenylbarbituric acid (PBS), 5-n-butylbarbituric acid (BBS), an organic peroxide and an amine, an amine and a sulfinic acid salt, an acidic compound and an aryl borate, barbituric acid and alkylborane, barbituric acid and alkyl ammonium chloride/copper chloride, 2,2'-azobis-(isobutyronitrile) (AIBN), 2,2'-azobis-(
• a photoactive agent such as, for example, 2 weight percent of 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (TPO) is added to the composition in order to make it light-curable.
• TPO 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide
• these polymerizable dental materials may include from about 0 to about 95 percent by weight filler particles. More preferably, these materials include from about 0 to about 85 percent by weight filler. Nanocomposites and ceramers may be used to make these composites/dental materials for this invention.
• the fillers preferably include both organic and inorganic particulate fillers to further reduce polymerization shrinkage, improve wear resistance and modify the mechanical and physical properties. Commercially available light curable resins and composites, heat or cold curable acrylics, resins or composites can also be used here.
• filler materials such as inorganic fillers, which can be naturally-occurring or synthetic, can be added to the printable polymerizable dental material and composition.
• Such materials include, but are not limited to, silica, titanium dioxide, iron oxides, silicon nitrides, glasses such as calcium, lead, lithium, cerium, tin, zirconium, strontium, barium, and aluminum- based glasses, borosilicate glasses, strontium borosilicate, barium silicate, lithium silicate, lithium alumina silicate, kaolin, quartz, and talc.
• the silica is in the form of silanized fumed silica.
• Preferred glass fillers are silanized barium boron aluminosilicate and silanized fluoride barium boron aluminosilicate.
• these surface treated inorganic fillers can be suspended in printable polymerizable resin. Most preferably, they form a homogeneous mixture.
• Organic particles such as poly(methyl methacrylate) (PMMA), highly crosslinked PMMA beads, poly(methyl/ethyl methacrylate), poly(methyl/butyl methacrylate), rubber modified PMMAs, rubber impact modifiers, crosslinked polyacrylates, thermoplastic and crosslinked polyurethanes, grounded polymerized compounds of this invention, polyethylene, polypropylene, polycarbonates and polyepoxides , and the like also can be used as fillers. These organic fillers can be added into printable polymerizable resin described above. Preferably, these organic fillers can dissolve or suspend in printable polymerizable resin. Most preferably, they form homogeneous colloids or homogeneous solution or suspension.
• PMMA poly(methyl methacrylate)
• highly crosslinked PMMA beads poly(methyl/ethyl methacrylate), poly(methyl/butyl methacrylate), rubber modified PMMAs, rubber impact modifiers, crosslinked polyacrylates, thermoplastic and crosslinked polyurethanes, grounded polymerized compounds of this
• Composite fillers such as dental composites can be polymerized and grounded or polymerized into particles and used in the formulations of this invention. Nanoparticles, fine glass particles, or other inorganic impregnated/modified PMMA or crosslinked polymer beads/particles from syntheses or grounding, surface treated or not, can also be used. These composite fillers can be selected based on specific printing resin systems for best compatibility and best bonding.
• the inorganic filler particles can also be surface-treated with a silane compound, other organic compound or coupling agent to improve bonding between the particles and resin matrix.
• Suitable silane compounds include, but are not limited to, gamma- methacryloxypropyltrimethoxysilane, gamma-mercaptopropyltriethoxysilane, gamma- aminopropyltrimethoxysilane, and combinations thereof.
• Suitable silane compounds include, but are not limited to, gamma-methacryloxypropyltrimethoxysilane, gamma-mercaptopropyltriethoxysilane, gamma- aminopropyltrimethoxysilane, and combinations thereof. Many methods, including several mechanical methods, ultrasonic dispersing method, etc. may be used to disperse pigments into resin matrix of this invention.
• organic pigments examples include Cromophtal Red-BRN 2-napthalenecarboxamide, azo pigments, polyazo pigments, azomethine pigments, isoindoline pigments, anthraquinone pigments, phthalocyanine pigments, benzimidazolone pigments, etc. More important, a PMMA or other polymer based pigments systems can be developed by encapsulating various pigments in fine PMMA polymer beads and form core shell structures, where pigment particles are encased in PMMA polymer beads, which are stable in resin matrix, especially MMA based polymerizable liquid. Resin based pigment systems can also be developed by encapsulating various pigments in various fine polymerized resin beads.
• polymer beads can be prepared by emulsion or suspension polymerizations.
• high pigment concentrated resins or MMA based resins can be polymerized and then grounded into fine powders and subsequently used in polymerizable liquids to form colloids or desirable suspensions.
• Pigmented materials are desirable because they have superior shade stability and stand up to UV light irradiation.
• This invention overcame the potential pigment separation from dental resins by dispersing the particles in the solution better to prevent settling and by milling the particles to smaller sizes. Mechanical methods were also applied to finely dispersed pigments in selected matrix, and polymeric additives so as to effectively stabilize and suspense pigments in liquid.
• This invention further overcame the potential pigment separation from dental resins by using nano-dispersed and fine inorganic and organic pigments. Nano-dispersed organic pigments are preferred to be used here.
• a fluorescing agent or several fluorescing agents may be included, such as Lumilux Blue LZ fluorescing agent (dihydroxy terepthalate acid ester).
• 3D printing methods can be used to build 3D dental devices, such as denture, denture base or splints containing two or more layered materials. These methods, e.g., fused deposition modeling (FDM), Ink-Jet printing using particulate powder layers in powder bed, selective laser sintering (SLS) or fiber reinforced extrusion from FDM can be used to build these dental devices, part of the dental devices, framework of dental devices or one or more layers of dental devices. A few methods will be discussed more in details below.
• FDM fused deposition modeling
• SLS selective laser sintering
• fiber reinforced extrusion from FDM can be used to build these dental devices, part of the dental devices, framework of dental devices or one or more layers of dental devices.
• dentin layer may be built layerwisely (thin layer by thin layer). If additional shaded dentin is desired, this denture can be removed and washed, and then can be inserted into a fourth vat containing different dentin shaded liquid and built another dentin layer. If additional shades are desired, this denture can be washed, and then can be inserted into a fifth vat containing enamel shaded liquid and subsequently enamel layer may be built layerwisely. Additional dentin and enamel shades can be built similarly as described above. Nevertheless, a denture may be built by reversal steps, where teeth or enamel are built first and then denture base.
• a polymerizable dental material was prepared by stirring at ambient temperature a liquid mixture of 20 grams of monomer made following the procedure of Example 2; 20 grams of triethylene glycol dimethacrylate; 5 grams of ethoxylated2 bisphenol A dimethacrylate (SR348 from Sartomer); 4 grams of tris(2-hydroxy ethyl) isocyanurate triacrylate (SR368 from Sartomer); 50 grams of silanated barium aluminoflurosilicate glass particles BAFG having an average particle size of from about 0.1 to about 10 micrometer; 0.975 grams of 2,4,6- trimethylbenzoyldiphenylphosphine oxide, (Lucirin TPO available from BASF); and 0.025 gram of butylated hydroxytoluene (BHT).
• This material can be used in DLP or SLA type 3D printer to make a layer or several layers of a dental device, such as multiple layered and multiple shaded artificial denture teeth of a denture.
• the present invention describes mainly denture and denture base; it should be understand that can be referred to splint, nightguard, retainer, aligner, flipper, flexible partial, and many other dental devices.

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• 2017
  • 2017-06-20 ES ES17735286T patent/ES2957886T3/es active Active
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